CN112225486B - Stable alkali-free liquid accelerator and preparation method and application thereof - Google Patents
Stable alkali-free liquid accelerator and preparation method and application thereof Download PDFInfo
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- CN112225486B CN112225486B CN202011114880.7A CN202011114880A CN112225486B CN 112225486 B CN112225486 B CN 112225486B CN 202011114880 A CN202011114880 A CN 202011114880A CN 112225486 B CN112225486 B CN 112225486B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/022—Carbon
- C04B14/026—Carbon of particular shape, e.g. nanotubes
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
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- Ceramic Engineering (AREA)
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Abstract
The stable alkali-free liquid accelerator comprises the following components in percentage by mass: aluminum sulfate: 25 to 40 percent; fluorine aluminum complex: 5 to 18 percent; early strength coagulation-promoting component: 0.5 to 8 percent; alcohol amine compound: 3 to 8 percent; modified carbon nanotube dispersion: 5 to 15 percent; dispersing agent: 0.5-2%; water: the balance; the invention also discloses a preparation method and application of the stable alkali-free liquid accelerator. The invention improves the early and later strength of the concrete, reduces the dosage of the alkaline pH regulator and is beneficial to the retention of the later strength of the concrete; the alkali-free accelerator disclosed by the invention is good in long-term stability, stable for 24 months in class under a normal temperature condition, and has the advantages of short setting time, high early strength, large retention rate of later strength and low injection resilience.
Description
Technical Field
The invention relates to an accelerator and a preparation method and application thereof, in particular to an alkali-free accelerator and a preparation method and application thereof.
Background
The accelerator is an additive capable of quickly setting and hardening cement concrete, and has become one of important component materials of sprayed concrete due to the remarkable advantages of the accelerator in the aspects of quick hardening and early strength since the accelerator is produced and used in the thirties of the last century. In the concrete spraying technology, the main purpose of adding the accelerating agent is to improve the thickness of a sprayed layer of sprayed concrete every time, shorten the interval of two spraying times, obviously improve the early strength of the concrete, reduce the later strength loss and further ensure the stability of the engineering quality. The accelerator is used as an important component material of sprayed concrete and widely applied to underground engineering, traffic engineering, hydraulic transportation engineering and some emergency repair engineering; in recent years, the function of the accelerator is becoming more and more important as the number of underground works increases on a large scale.
The accelerator is mainly divided into alkaline powder accelerator and alkali-free liquid accelerator. The alkaline powdery accelerator and the alkaline liquid accelerator have the following problems in the construction process: firstly, although the early strength of the cement concrete is improved, the later strength loss is serious; secondly, the higher alkali content can damage the health of constructors on one hand, and on the other hand, the too high alkali content can cause the alkali aggregate reaction of concrete, thereby greatly reducing the strength and durability of the concrete; thirdly, the rebound quantity of the concrete after construction is large and the wet operation is not facilitated. The alkali-free accelerator solves the problems well, has the advantages of no corrosion, high later strength retention rate, safety, no pollution and the like, but the existing alkali-free liquid accelerator generally has the problems of poor stability, strong acidity, large loss of later mechanical property and durability of concrete caused by the low-alkali accelerator mainly comprising aluminate and the like.
CN107954628A discloses an alkali-free chlorine-free sulfate radical-free liquid accelerator which is composed of aluminum dihydrogen phosphate, an organic alcohol amine accelerating component, an inorganic fluorine-containing accelerating component, an alkali thickening rheological additive component, an antifreeze agent component and water. The scheme takes the aluminum dihydrogen phosphate as a raw material to provide aluminum ions, and the aluminum dihydrogen phosphate is synthesized by phosphoric acid and aluminum hydroxide, and has the defects that: the process is complicated and the cost is too high compared with the accelerator which takes aluminum sulfate as the main component.
CN105174790A discloses an alkali-free liquid cement accelerator and a use method thereof, wherein the cement accelerator comprises the following components in parts by weight: 40-45 parts of aluminum sulfate, 5-10 parts of aluminum trifluoride, 0.2-0.5 part of a tackifying component, 4-9 parts of a reinforcing material, 3-7 parts of an organic substance and 50-60 parts of water.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a stable alkali-free liquid accelerator with low cost, good stability and good accelerating effect, and a preparation method and application thereof.
The technical scheme adopted by the invention for solving the technical problem is as follows: a stable alkali-free liquid accelerator comprises the following components in percentage by mass:
aluminum sulfate: 25 to 40 percent;
fluorine aluminum complex: 5 to 18 percent;
early strength coagulation-promoting component: 0.5 to 8 percent;
alcohol amine compound: 3 to 8 percent;
modified carbon nanotube dispersion: 5 to 15 percent;
dispersing agent: 0.5-2%;
water: the balance;
the sum of the mass percentages of the components is 100 percent.
Preferably, the fluorine aluminum complex is a mixture of hydrofluoric acid and aluminum hydroxide; the mass ratio of the hydrofluoric acid to the aluminum hydroxide is 1: 1.1-1.3.
Preferably, the early strength coagulation promoting component is one or more of calcium fluoride, calcium formate, magnesium carbonate and magnesium sulfate.
Preferably, the alkanolamine compound is one or more than two of diethanolamine, triethanolamine, triisopropanolamine and diethanolisopropanolamine.
Preferably, the dispersant is any one of hydrated magnesium silicate, polyethylene glycol and polyacrylamide.
Preferably, the mass concentration of the modified carbon nanotube dispersion liquid is 8.0-12.0 g/L, and the modified carbon nanotube dispersion liquid is prepared by adding water to modified carbon nanotubes.
Preferably, the modified carbon nanotube is modified with sodium hydroxide.
Preferably, the preparation method of the modified carbon nanotube dispersion liquid comprises the following steps: adding water into the powdery carbon nanotubes to prepare a carbon nanotube solution, adding a sodium hydroxide solution under the condition of stirring, heating for reaction, and filtering to obtain powder precipitate; washing the powder precipitate with water until the washed washing liquid is neutral, and drying to obtain modified carbon nanotube powder; and adding water into the modified carbon nanotube powder to prepare a solution, and performing ultrasonic dispersion for 30-60min to obtain a modified carbon nanotube dispersion solution.
More preferably, the concentration of the carbon nanotube solution is 8.0 to 12.0 g/L, and still more preferably 9.0 to 11.0 g/L.
More preferably, the temperature of the heating reaction is 40-60 ℃.
More preferably, the heating reaction time is 2 to 4 hours.
More preferably, the concentration of the sodium hydroxide solution is 10-30 wt%, and the mass ratio of the sodium hydroxide to the carbon nanotubes is 2-4: 1.
The preparation method of the stable alkali-free liquid accelerator comprises the following steps:
(1) preparation of the fluorine aluminum complex: mixing water and hydrofluoric acid in a reaction vessel, stirring, adding aluminum hydroxide, and reacting under heat preservation to generate a fluorine-aluminum complex;
(2) adding aluminum sulfate, an early strength coagulation accelerating component and an alcohol amine compound into the reaction container, and carrying out heat preservation reaction; cooling, adding a dispersing agent, and carrying out heat preservation reaction; cooling to room temperature to obtain a base solution of the accelerating agent;
(3) and (3) mixing the modified carbon nanotube dispersion liquid with the accelerator base liquid prepared in the step (2), dispersing, and adding water for uniformly mixing.
Preferably, in the step (1), the concentration of the hydrofluoric acid is 20-25wt%, and the mass ratio of the hydrofluoric acid to the aluminum hydroxide is 1: 1.1-1.3.
Preferably, in the step (1), the mass ratio of the water to the hydrofluoric acid is 0.85-1: 1.
Preferably, in the step (1), the temperature of the heat preservation reaction is 50-60 ℃, and the time of the heat preservation reaction is 2-4 hours.
Preferably, in the step (2), the temperature of the heat preservation reaction is 40-50 ℃, the time of the heat preservation reaction is 2-2.5 hours, the temperature is reduced to 30-35 ℃, and the time of the heat preservation reaction after the dispersant is added is 30-60 min.
Preferably, in the step (3), the rotation speed of the dispersing machine is 5000-.
The dosage of the stable alkali-free liquid accelerator used in the sprayed concrete is 6-9 wt% of the mass of the concrete cementing material.
The invention has the following beneficial effects:
(1) the invention uses the one-dimensional nano material modified carbon nano tube as the alkali-free liquid accelerator; the steric hindrance effect of an accelerator system is enhanced by utilizing the specific large specific surface area, high modulus and high strength of the modified carbon nano tube and the nano coaxial circular tube structure, and the early and later strength of the concrete is improved;
(2) the modified carbon nano tube dispersion liquid containing a large number of hydroxyl groups is simultaneously used as a pH regulator of the accelerator, so that the using amount of an alkaline pH regulator can be reduced, the requirement of the accelerator on an alkali-free accelerator in national standards is met, and the later strength of concrete is favorably maintained;
(3) the prepared alkali-free accelerator has good long-term stability and 24 months of stability when stored at normal temperature in class by utilizing the synergistic thickening and dispersing effects between the modified carbon nanotube dispersion liquid and the dispersing agent;
(4) the stable alkali-free liquid accelerator prepared by the preparation method has the advantages of short setting time, high early strength, high retention rate of later strength and low injection resilience rate, and can be widely applied to supporting, leaking stoppage, repairing and the like of tunnels, highways, railways, mines and subways.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The starting materials used in the examples of the present invention were all obtained from conventional commercial sources.
Example 1
The stable alkali-free liquid accelerator comprises the following raw materials:
aluminum sulfate: 30.9 percent;
fluorine aluminum complex: 17.8 percent;
early strength accelerating component (calcium fluoride): 5.2 percent;
alcamines (triethanolamine): 3.2 percent;
modified carbon nanotube dispersion: 6.4 percent;
dispersing agent: (polyacrylamide) 0.5%;
water: the balance;
the sum of the mass percentages of the components is 100 percent.
The preparation method of the modified carbon nanotube dispersion liquid comprises the following steps:
adding water into the powdery carbon nanotubes to prepare 0.5L of carbon nanotube solution with the mass concentration of 10.0 g/L, keeping stirring, heating to 40 ℃, then adding 100g of 10wt% NaOH solution for reaction, carrying out heat preservation reaction for 2 hours, filtering, repeatedly washing the powder obtained after filtering with deionized water until the washing liquid after washing is neutral; drying the washed powder at constant temperature to obtain modified carbon nanotube powder; the modified carbon nano tube powder is added with deionized water to prepare a solution with the mass concentration of 10.0 g/L, and the modified carbon nano tube dispersion with the mass concentration of 10.0 g/L is obtained after ultrasonic dispersion for 40 min.
The preparation method of the stable alkali-free liquid accelerator comprises the following steps:
(1) preparation of the fluorine aluminum complex: adding 60.00g of hydrofluoric acid and 60g of bottom water into a reaction kettle, starting a stirring device, controlling the temperature of the reaction kettle to be 55 ℃, adding 78.00g of aluminum hydroxide twice, and carrying out heat preservation reaction for 2 hours to generate a fluorine aluminum complex;
(2) 240.00g of aluminum sulfate, 40.00g of calcium fluoride and 25.00g of triethanolamine are added into a reaction kettle, and the reaction is carried out for 2.5 hours at the temperature of 45 ℃; cooling to 30 ℃, adding 4.00g of polyacrylamide, keeping the temperature for reaction for 30min, and cooling to room temperature to obtain accelerator base liquid;
(3) and (3) mixing 50.00g of modified carbon nanotube dispersion liquid with the accelerator base liquid prepared in the step (2), dispersing at a high speed of 5000r/min for 70min, supplementing 220g of water, and uniformly mixing.
Example 2
The stable alkali-free liquid accelerator comprises the following raw materials:
aluminum sulfate: 26.2 percent;
fluorine aluminum complex: 16.9 percent;
early strength accelerating component (magnesium carbonate): 4.6 percent;
alcamines (triisopropanolamine): 3.4 percent;
modified carbon nanotube dispersion: 6.8 percent;
dispersing agent: (polyethylene glycol) 1.1%;
water: the balance;
the sum of the mass percentages of the components is 100 percent.
The preparation method of the modified carbon nanotube dispersion liquid comprises the following steps:
adding water into the powdery carbon nanotubes to prepare 0.5L of carbon nanotube solution with the mass concentration of 8.0 g/L, keeping stirring, heating to 50 ℃, then adding 50g of 25wt% NaOH solution for reaction, carrying out heat preservation reaction for 3 hours, filtering, repeatedly washing the powder obtained after filtering with deionized water until the washing liquid after washing is neutral; drying the washed powder at constant temperature to obtain modified carbon nanotube powder; the modified carbon nano tube powder is added with deionized water to prepare a solution with the mass concentration of 10.0 g/L, and the modified carbon nano tube dispersion with the mass concentration of 10.0 g/L is obtained after ultrasonic dispersion for 30 min.
The preparation method of the stable alkali-free liquid accelerator comprises the following steps:
(1) preparation of the fluorine aluminum complex: adding 70.00g of hydrofluoric acid and 60g of bottom water into a reaction kettle, starting a stirring device, controlling the temperature of the reaction kettle to be 60 ℃, adding 78.00g of aluminum hydroxide twice, and carrying out heat preservation reaction for 3 hours to generate a fluorine aluminum complex;
(2) 230.00g of aluminum sulfate, 40.00g of magnesium carbonate and 30.00g of triisopropanolamine are added into a reaction kettle, and the reaction is carried out for 2.5 hours at the temperature of 40 ℃; cooling to 30 ℃, adding 10.00g of polyethylene glycol, keeping the temperature for reaction for 30min, and cooling to room temperature to obtain accelerator base liquid;
(3) and (3) mixing 60.00g of modified carbon nano tube dispersion liquid with the accelerator base liquid prepared in the step (2), dispersing at a high speed of 6000r/min for 60min, supplementing 300g of water, and mixing uniformly to obtain the accelerator base liquid.
Example 3
The stable alkali-free liquid accelerator comprises the following raw materials:
aluminum sulfate: 30.2 percent;
fluorine aluminum complex: 17.7 percent;
early strength accelerating component (magnesium sulfate): 4.5 percent;
alkanolamine compound (diethanolamine): 3.9 percent;
modified carbon nanotube dispersion: 7.1 percent;
dispersing agent: (magnesium silicate hydrate) 1.9%;
water: the balance;
the sum of the mass percentages of the components is 100 percent.
The preparation method of the modified carbon nanotube dispersion liquid comprises the following steps: the same as in example 2.
The preparation method of the stable alkali-free liquid accelerator comprises the following steps:
(1) preparation of the fluorine aluminum complex: adding 60.00g of hydrofluoric acid and 60g of bottom water into a reaction kettle, starting a stirring device, controlling the temperature of the reaction kettle to be 60 ℃, adding 78.00g of aluminum hydroxide twice, and carrying out heat preservation reaction for 2.5 hours to generate a fluorine-aluminum complex;
(2) adding 235.00g of aluminum sulfate, 35.00g of magnesium sulfate and 30.00g of diethanolamine into a reaction kettle, and carrying out heat preservation reaction at 45 ℃ for 2 hours; cooling to 35 ℃, adding 15.00g of hydrated magnesium silicate, keeping the temperature for reaction for 30min, and cooling to room temperature to obtain accelerator base liquid;
(3) and (3) mixing 55.00g of modified carbon nanotube dispersion liquid with the accelerator base liquid prepared in the step (2), dispersing at a high speed of 7000r/min for 80min, adding 210 g of water, and uniformly mixing to obtain the accelerator base liquid.
Example 4
The stable alkali-free liquid accelerator comprises the following raw materials:
aluminum sulfate: 28.6 percent;
fluorine aluminum complex: 17.3 percent;
early strength accelerating component (calcium formate): 4.2 percent;
alkanolamines (diethanolisopropanolamine): 4.2 percent;
modified carbon nanotube dispersion: 7.7 percent;
dispersing agent: (polyethylene glycol) 1.2%;
water: the balance;
the sum of the mass percentages of the components is 100 percent.
The preparation method of the modified carbon nanotube dispersion liquid comprises the following steps: the same as in example 1.
The preparation method of the stable alkali-free liquid accelerator comprises the following steps:
(1) preparation of the fluorine aluminum complex: adding 65.00g of hydrofluoric acid and 60g of bottom water into a reaction kettle, starting a stirring device, controlling the temperature of the reaction kettle to be 55 ℃, adding 80.00g of aluminum hydroxide twice, and carrying out heat preservation reaction for 3 hours to generate a fluorine aluminum complex;
(2) 240.00g of aluminum sulfate, 35.00g of calcium formate and 35.00g of diethanol monoisopropanolamine are added into a reaction kettle, and the reaction is carried out for 2.5 hours at the temperature of 40 ℃; cooling to 30 ℃, adding 10.00g of polyethylene glycol, keeping the temperature for reaction for 30min, and cooling to room temperature to obtain accelerator base liquid;
(3) and (3) mixing 65.00g of modified carbon nano tube dispersion liquid with the accelerator base liquid prepared in the step (2), dispersing at a high speed of 8000r/min for 80min, supplementing 250 g of water, and mixing uniformly to obtain the accelerator base liquid.
Example 5
The stable alkali-free liquid accelerator comprises the following raw materials:
aluminum sulfate: 30.2 percent;
fluorine aluminum complex: 18.0 percent;
early strength accelerating component (calcium fluoride): 4.3 percent;
alcamines (triethanolamine): 3.7 percent;
modified carbon nanotube dispersion: 7.4 percent;
dispersing agent: (polyacrylamide) 0.6%;
water: the balance;
the sum of the mass percentages of the components is 100 percent.
The preparation method of the modified carbon nano tube dispersion liquid comprises the following steps: the same as in example 1.
The preparation method of the stable alkali-free liquid accelerator comprises the following steps:
(1) preparation of the fluorine aluminum complex: adding 68.00g of hydrofluoric acid and 60g of bottom water into a reaction kettle, starting a stirring device, controlling the temperature of the reaction kettle to be 60 ℃, adding 78.00g of aluminum hydroxide twice, and carrying out heat preservation reaction for 3.5 hours to generate a fluorine-aluminum complex;
(2) 245.00g of aluminum sulfate, 35.00g of calcium fluoride and 30.00g of triethanolamine are added into a reaction kettle, and the reaction is carried out for 2 hours at the temperature of 45 ℃; cooling to 35 ℃, adding 5.00g of polyacrylamide, keeping the temperature for reaction for 30min, and cooling to room temperature to obtain accelerator base liquid;
(3) and (3) mixing 60.00g of modified carbon nanotube dispersion liquid with the accelerator base liquid prepared in the step (2), dispersing at a high speed of 7000r/min for 70min, adding 230 g of water, and uniformly mixing to obtain the accelerator base liquid.
The stable alkali-free liquid accelerator prepared in the examples 1 to 5 was tested according to the following relevant standards:
GB T8077-2012 test method for homogeneity of concrete admixture;
GBT 35159 and 2017 accelerator for shotcrete.
The stable alkali-free liquid accelerator prepared in the embodiment 1-5 and the alkali-free liquid accelerator sold in the market at present (sample 1 purchased from a factory in the north of lake) are subjected to a comparison test, which comprises a primary and final setting time test and a compressive strength test of cement mortar, wherein the primary and final setting time test and the compressive strength test are carried out on the liquid alkali-free accelerator according to the standard' accelerator for spraying concrete in GBT 35159-;
the materials used for the setting time test were: 400g of cement, 140g of water (containing water contained in the alkali-free liquid accelerator), wherein the mixing amount of the alkali-free liquid accelerator is 6 percent of the cement;
the materials used in the compressive strength test are as follows: 900g of cement, 450g of water (containing water of the alkali-free liquid accelerator) and 1350g of standard sand;
the test results of cement paste setting time, mortar strength and stability are shown in tables 1 and 2.
TABLE 1 Cement paste setting time test results
TABLE 2 Cement mortar Strength testing and stability
As can be seen from tables 1 and 2, the stable alkali-free liquid accelerator has shorter initial setting time and final setting time than the commercial products, higher retention rate of 1d compressive strength, 28d compressive strength and 90d compressive strength and better stability.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention, so that any modifications, equivalents and improvements made by the present invention as described in the specification are included in the scope of the present invention.
Claims (9)
1. The stable alkali-free liquid accelerator is characterized by comprising the following components in percentage by mass:
aluminum sulfate: 25 to 40 percent;
fluorine aluminum complex: 5 to 18 percent;
early strength coagulation-promoting component: 0.5 to 8 percent;
alcohol amine compound: 3 to 8 percent;
modified carbon nanotube dispersion: 5 to 15 percent;
dispersing agent: 0.5-2%;
water: the balance;
the sum of the mass percentages of the components is 100 percent;
the dispersing agent is any one of hydrous magnesium silicate, polyethylene glycol and polyacrylamide;
modifying the modified carbon nano tube by adopting sodium hydroxide;
the mass concentration of the modified carbon nanotube dispersion liquid is 8.0-12.0 g/L, and the modified carbon nanotube dispersion liquid is prepared by adding water into modified carbon nanotubes;
the preparation method of the modified carbon nanotube dispersion liquid comprises the following steps: adding water into the powdery carbon nanotubes to prepare a carbon nanotube solution, adding a sodium hydroxide solution under the stirring condition, heating for reaction, and filtering to obtain powder precipitate; washing the powder precipitate with water until the washed washing liquid is neutral, and drying to obtain modified carbon nanotube powder; and adding water into the modified carbon nanotube powder to prepare a solution, and performing ultrasonic dispersion for 30-60min to obtain a modified carbon nanotube dispersion solution.
2. The stable alkali-free liquid accelerator according to claim 1, wherein the fluorine aluminum complex is a mixture of hydrofluoric acid and aluminum hydroxide; the mass ratio of the hydrofluoric acid to the aluminum hydroxide is 1: 1.1-1.3.
3. The stable alkali-free liquid accelerator as claimed in claim 1 or 2, wherein the early strength accelerating component is one or more of calcium fluoride, calcium formate, magnesium carbonate and magnesium sulfate; the alcohol amine compound is one or more than two of diethanol amine, triethanol amine, triisopropanol amine and diethanol monoisopropanol amine.
4. The stable alkali-free liquid accelerator according to claim 1 or 2, wherein the concentration of the carbon nanotube solution is 8.0 to 12.0 g/L; the temperature of the heating reaction is 40-60 ℃; the heating reaction time is 2-4 hours; the concentration of the sodium hydroxide solution is 10-30 wt%; the mass ratio of the sodium hydroxide to the carbon nano tube is 2-4: 1.
5. The stable alkali-free liquid accelerator according to claim 3, wherein the concentration of the carbon nanotube solution is 8.0-12.0 g/L; the temperature of the heating reaction is 40-60 ℃; the heating reaction time is 2-4 hours; the concentration of the sodium hydroxide solution is 10-30 wt%; the mass ratio of the sodium hydroxide to the carbon nano tube is 2-4: 1.
6. The method for preparing a stabilized alkali-free liquid accelerator according to any one of claims 1 to 5, comprising the steps of:
(1) preparation of the fluorine aluminum complex: mixing water and hydrofluoric acid in a reaction vessel, stirring, adding aluminum hydroxide, and reacting under heat preservation to generate a fluorine-aluminum complex;
(2) adding aluminum sulfate, an early strength coagulation accelerating component and an alcohol amine compound into the reaction container, and carrying out heat preservation reaction; cooling, adding a dispersing agent, and carrying out heat preservation reaction; cooling to room temperature to obtain a base solution of the accelerating agent;
(3) and (3) mixing the modified carbon nanotube dispersion liquid with the accelerator base liquid prepared in the step (2), dispersing, and adding water for uniformly mixing.
7. The preparation method of the stable alkali-free liquid accelerator according to claim 6, wherein in the step (1), the concentration of the hydrofluoric acid is 20-25wt%, and the mass ratio of the hydrofluoric acid to the aluminum hydroxide is 1: 1.1-1.3; in the step (1), the mass ratio of water to hydrofluoric acid is 0.85-1: 1; in the step (1), the temperature of the heat preservation reaction is 50-60 ℃, and the time of the heat preservation reaction is 2-4 hours.
8. The preparation method of the stable alkali-free liquid accelerator according to claim 6 or 7, wherein in the step (2), the temperature of the heat preservation reaction is 40-50 ℃, the time of the heat preservation reaction is 2-2.5 hours, the temperature is reduced to 30-35 ℃, and the time of the heat preservation reaction after the dispersant is added is 30-60 min; in the step (3), the rotation speed of the dispersing machine is 5000-.
9. The use of the stabilized alkali-free liquid accelerator as claimed in any one of claims 1 to 5, wherein the amount used in the sprayed concrete is 6 to 9 wt% of the mass of the concrete cement.
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